Mordenite-based catalyst containing at least one metal from group viii and its use for isomerizing a c8 aromatic fraction

ABSTRACT

The invention relates to a catalyst for isomerizing a C 8  aromatic fraction containing a mordenite and at least one metal from group VIII of the periodic classification of elements (such as Pt or Pd), characterized in that the mordenite is such that its skeleton Si/Al atomic ratio is between 6 and 10.5, its sodium weight content is below 2000 ppm, its unit cell volume is between 2.73 and 2.78 nm 3 , its benzene adsorption capacity is between 4 and 10% based on the dry mordenite weight and its 1,3,5-trimethylbenzene adsorption capacity is between 0.5 and 2.5% by weight based on the dry mordenite weight. The invention also relates to the preparation of said mordenite.

This is a division of application Ser. No. 07/417,143, filed Oct. 4,1989, now U.S. Pat. No. 5,077,254.

The present invention relates to an aluminosilicate-type catalystincorporating a mordenite, whereof the size of the channels andconsequently its geometrical selectivity has been modified in acontrolled manner by heat and/or chemical treatments, at least one metalof group VIII of the periodic classification of elements (Handbood ofChemistry and Physics, 6th edition, 1980/1) and optionally a matrix andits use in isomerization reactions of C₈ aromatic hydrocarbons.

At present, the catalysts industrially used in these reactions areessentially the zeolite ZSM5, used alone or optionally mixed with otherzeolites, such as e.g. mordenite. These catalysts are more particularlydescribed in U.S. Pat. Nos. 4,467,129, 4,482,773 and EP-B-0138617.

The interest of ZSM5 is based on its excellent form selectivity, whichleads to a high para-xylene selectivity, due to the size of itschannels, which only permit the passage of xylenes and in particularprevent the formation of trimethylbenzene. However, it still has arelatively low activity.

Mordenite is a highly active zeolite, particularly in isomerizationreactions of C₈ aromatic fractions and is in particular more active thanzeolites of structure MFI. However, it is not very selective, thedismutation reaction of the xylenes into trimethylbenzenes and intotoluene being very considerable. As a result of the present invention,it is possible to obtain by heat and/or chemical treatments (acid), amordenite having isomerization performance characteristics (and inparticular an isomerization yield) at least equivalent to those ofcatalysts with a MFI structure and with which consequently the secondaryreactions, such as in particular dismutation, are considerably reduced.

The zeolite used in the catalyst according to the present invention isproduced from a so-called "small pore" mordenite, whose sodium weightcontent is generally between 4 and 6.5%, whose skeleton Si/Al atomicratio is generally between 4.5 and 6.5 and whose unit cell volume isgenerally between 2.77 and 2.80 nm³ (with 1 nm=10⁻⁹ m). This mordeniteconventionally only adsorbs molecules with a kinetic diameter belowapproximately 4.4×10⁻¹⁰ m.

This small pore mordenite firstly undergoes an exchange reaction makingit possible to replace the sodium cations by ammonium cations. Thisexchange is carried out by immersing the mordenite in an ionizableammonium salt solution, e.g. using ammonium nitrate, which has amolarity generally exceeding 0.5 and at a temperature normally between20° and 150° C. This exchange stage can be repeated several times andcan optionally be followed by one or more washing stages. The sodiumweight content of the mordenite obtained in this way is generally below0.2% and preferably below 0.12%. Its unit cell volume and its Si/Alatomic ratio remains substantially unchanged. Its benzene adsorptioncapacity is approximately 1% by weight based on the dry mordenite weightand it only has a very limited trimethylbenzene adsorption. Its waterweight content is between 5 and 40% and preferably between 10 and 30%.

According to the invention, the mordenite obtained with the water weightcontent indicated hereinbefore, must undergo various treatments and inparticular either at least one calcination under a dry air stream, whichmay or may not be followed by at least one acid action, or at least onedirect acid action, particularly to at least partly clear or unblock itsstructure.

The term calcination under a dry air stream is understood to mean a heattreatment, performed under very precise temperature, air water contentand air flow rate conditions, which makes it possible to leave the steamgiven off by the solid sufficiently in contact with said solid for it toact on the structure and to remove the aluminium from the skeleton to agreater or lesser extent as a function of the calcination temperatureused. This aluminium removal from the skeleton by continuous eliminationof the aluminum atoms in the tetrahedral position leads, in the case ofthe small pore mordenite used in the invention, to an unblocking of theporosity which can be controlled by controlling the calcinationtemperature.

The calcination conditions used in preferred manner in the presentinvention are a water weight content in the air (prior to its contactwith the solid) below 1% and preferably below 300 ppm, an air flow ratebetween 0.5 and 10 liters/hour/gramme of solid and preferably between 1and 5 liters/hour/gramme of solid (1/h/g), a calcination temperaturebetween approximately 450° and approximately 650° C. and preferablybetween approximately 450 ° and approximately 580° C. and a temperaturerise rate between 2° and 8° C./minute and preferably between 3° and 6°C./minute.

The final calcination temperature will generally be maintained forapproximately 0.5 to approximately 5 hours and preferably forapproximately 1 to approximately 4 hours.

The thermal calcination treatment under a dry air stream can optionallybe followed by at least one (gentle) acid action operation making itpossible to eliminate the aluminium ions in the octahedral positionwithout affecting the aluminium ions of the skeleton. For this purpose,following calcination, the solid is heated in a mineral or organic acidsolution, such as e.g. hydrochloric or nitric acid, with a normalitynormally below 2N and preferably below 0.5N, at a temperature belowapproximately 100° C. and preferably below approximately 60° C. Thisgenerally lasts for approximately 4 hours and with a H_(s) ⁺ /Al_(z)ratio between 8.5 and 11.5 and preferably equal to 10, in which H_(s) ⁺is the number of proton moles in solution and Al_(z) is the number ofaluminium cation moles in the mordenite.

The mordenite according to the invention can also be obtained by atleast one direct acid action process, which consists of heating, to atemperature exceeding approximately 70° C. and preferably exceedingapproximately 85° C., the zeolite following the cationic exchange stage(and optionally washing) in an organic or mineral acid solution, such ase.g. hydrochloric or nitric acid, with a normality conventionallybetween 0.1 and 5N and preferably between 0.2 and 3N, for in generalapproximately 2 hours, with a H_(s) ⁺ /Al_(z) ratio between 5 and 20 andpreferably between 8 and 15, in which H_(s) ⁺ is the number of protonmoles in the solution and Al_(z) the number of aluminium cation moles inthe mordenite. So there is an extraction of the aluminum cations both inthe tetrahedral and octahedral positions and consequently an unblockingof the porosity which increases with the intensity of the acid action.

The mordenite obtained by one of the preceding treatments has a unitcell volume between 2.73 and 2.78 nm³. Its skeleton Si/Al atomic ratiois between 6 and 10.5 and preferably between 6 and 9.5. The sodiumweight ratio of said mordenite is generally below 2000 ppm and ispreferably below 1000 ppm. Its benzene adsorption capacity varies from 4to 10% and preferably 5 to 9% by weight based on the dry mordeniteweight and its 1,3,5-trimethylbenzene adsorption capacity is 0.5 to2.5%, preferably 0.7 to 2% by weight based on the dry mordenite weight.

The mordenites contained in the catalysts according to the inventionconsequently have the special feature of being able to adsorb relativelylarge benzene quantities, but of only very slightly adsorbing1,3,5-trimethylbenzene, which is a product formed during the undesirabledismutation reaction of xylenes. Their adsorption capacities are ingeneral determined by gravimetry, e.g. in accordance with the followingmethod: A sample of the mordenite is previously desorbed at 300° C.under 10⁻⁴ Torr (133.32×10⁻⁴ Pa), adsorption then being carried out forat least 4 hours under the following conditions:

for benzene adsorption:

T=30° C.

P=28 Torr (3733 Pa)

P/Ps=0.25

for the 1,3,5-trimethylbenzene adsorption:

T=50° C.

P=3 Torr (400 Pa)

P/Ps=0.26

in which Ps represents the saturated steam pressure at the temperatureof the experiment. The adsorbed volumes are calculated on the basis ofthe density of the adsorbate in liquid form at the adsorptiontemperature: d_(o) =0.868 for benzene and d_(o) =0.839 for1,3,5-trimethylbenzene.

The other characteristics can be measured by the following methods:

the skeleton Si/Al atomic ratios are determined by infrared spectrometryand the sodium contents by atomic adsorption;

the unit cell volume is determined by X-defraction, the mordenite samplebeing prepared in an identical way to the operating procedure of ASTM DStandard 3942 80 for faujasite.

The thus modified mordenite can then be subjected as it is to thedeposition of at least one group VIII metal, preferably chosen from thegroup formed by platinum and palladium, and shaped by all knownprocedures. It can in particular be mixed with a generally amorphousmatrix, e.g. a humid alumina gel powder. The mixture is then shaped,e.g. by extrusion through a die. The mordenite content of the support(mordinite+matrix) obtained in this way is generally betweenapproximately 0.5 and 99.99% and advantageously between 40 and 90% byweight, based on the support. It is more particularly betweenapproximately 60 and 85% by weight, based on the support. The matrixcontent of the catalyst is advantageously between approximately 10 and60% and preferably between approximately 15 and 40% by weight, based onthe support (mordenite+matrix).

The shaping can be carried out with matrixes other than alumina, such ase.g. magnesia, silica-alumina, natural clays (kaolin, bentonite) and bymethods other than extrusion, such as pellet or dragee formation.

The hydrogenating metal of group VIII, preferably Pt and/or Pd, is thendeposited on the support by any known process permitting the depositionof metal on mordenite. It is possible to use the cation exchange methodwith competition, in which the competing agent is preferably ammoniumnitrate, the competition ratio being at least equal to approximately 50and advantageously approximately 50 to 200. In the case of platinum orpalladium, it is standard practice to use a tetrammine complex ofplatinum or a tetrammine complex of palladium. The latter would then besubstantially entirely deposited on the mordenite. This cation exchangemethod can also be used for directly depositing the metal on themordenite powder before its possible mixing with a matrix.

The deposition of the metal (or metals) is generally followed by acalcination under air or oxygen, usually at between 300° and 600° C. for0.5 to 10 hours and preferably at 350° to 550° C. for 1 to 4 hours. Itis then possible to carry out reduction under hydrogen, generally at atemperature between 300° and 600° C. for 1 to 10 hours and preferably350° to 550° C. for 2 to 5 hours. The content of the metal of group VIII(Pt and/or Pd) deposited on the catalyst and obtained following theexchange is between 0.05 and 1.5% and preferably between 0.1 and 1% byweight, based on the total catalyst.

The platinum or palladium may also be deposited on the alumina binderand not directly on the mordenite, before or after the shaping stage, bycarrying out an anion exchange with hexachloroplatinic acid,hexachloropalladic acid and/or palladium chloride in the presence of acompeting agent, e.g. hydrochloric acid. Prior to the deposition of theplatinum and/or palladium, as hereinbefore, the catalyst undergoes acalcination, generally at between 300° and 600° C. and is then reducedunder hydrogen in the aforementioned manner.

The bifunctional catalyst obtained by the above procedures can be usedin the isomerization reactions of a C₈ aromatic fraction, e.g.comprising either solely a mixture of xylenes, or a mixture of xylenesand ethyl benzene. The isomerization of the alkyl aromatics and inparticular xylenes has a considerable commerical importance. Generallypara-xylene is the most sought product, because it is used as anintermediate in the production of polyester fibres. Preference is givento the production of para-xylene by isomerizing meta-xylene, which canbe obtained by the isomerization of ortho-xylene. The ethyl benzene,which is difficult to separate by distillation from the mixture ofxylenes (the boiling points of the different compounds being very closeto one another), very frequently occurs in the isomerization charge ofthe C₈ aromatics.

The operating conditions for the isomerization process are generally asfollows:

temperature between 240° and 600° C., preferably between 350° and 510°C,

pressure between 0.5 and 100 bars, preferably between 2 and 30 bars,

space velocity (pph), in charge mass per catalyst charge unit and perhour, between 0.5 and 200 and preferably between 5 and 100,

molar ratio of hydrogen to hydrocarbons in the charge (H₂ /HC) between0.5 and 12 and preferably between 2 and 6.

The following examples illustrate the invention without limiting itsscope. They are given for a charge formed from 75% ortho-xylene and 25%ethyl benzene (by weight).

EXAMPLE 1 Catalyst A according to the invention

The starting substance is a small pore mordenite called Alite 150 of theSociete Chimique de la Grande Paroisse. Its chemical formula in theanhydrous state is Na A10₂ (SiO₂)₅.5 and its benzene adsorption capacityis 1% by weight, based on the dry solid weight (unit cell volume: 2.79nm³ ; sodium content: 5.3% by weight; kinetic diameter of adsorbedmolecules: 3.8×10⁻¹⁰ m). 50 g of this poweder are immersed in a 2Mammonium nitrate solution and the solution heated to 95° C. for twohours.

The volume of the ammonium nitrate solution used is equal to four timesthe dry zeolite weight (vol/wt=4). This cation exchange operation isrepeated three times. After the third exchange, the product is washedwith water at 20° C. for 20 minutes with a vol/wt ratio of 4. The sodiumcontent, expressed as a weight percentage based on the dry solid weight,passes from 5.5 to 0.1%. The product is then filtered and undergoescalcination under a dry air stream, whose water weight content is below300 ppm, at approximately 550° C. and for 2 hours.

For this purpose, 2 g of powder (mordenite with a water weight contentof approximately 25%) in the form of ammonium are fed into a diameter 30mm quartz reactor. The powder bed formed is traversed by a dry air flowof 2 1/h. The temperature rise rate is 4.2° C./min. Once the temperaturereaches 550° C., the temperature is maintained at this level for 2hours.

The thus obtained mordenite has a skeleton Si/Al atomic ratio of 7.5.Its sodium weight content is 1000 ppm. Its unit mesh volume is 2.76 nm³.Its benzene adsorption capacity is 8% by weight, based on the drymordenite weight and its 1,3,5-trimethylbenzene adsorption capacity is1.8% by weight, based on the dry mordenite weight.

Intimate mixing then takes place between said mordenite and the alumina,on which has been dispersed 0.3% by weight of platinum, the supportconstituted by the mordenite-alumina mixture containing 40% by weightalumina. The platinum weight content of the final catalyst A istherefore 0.12%.

The thus produced catalyst is shaped by pelletizing, calcined under airup to 500° C. for 2 hours and reduced under hydrogen at 500° C. for 3hours.

Catalyst A is then tested in the isomerization of the mixture oforthoxylene (75% by weight) and ethylbenzene (25% by weight), at 420°C., under 15 bars and with a space velocity (pph) of 50 (hour)⁻¹ and amolar ratio of hydrogen to hydrocarbon (H₂ /HC) of approximately 4.

The performance characteristics of catalyst A (and catalyst prepared inthe following examples), given in Table I, are defined by: ##EQU1##

EXAMPLE 2 Catalyst B according to the invention

Catalyst B differs from catalyst A prepared in Example 1 in thatfollowing the calcination stage under a dry air stream, the mordeniteundergoes gentle acid action consisting of heating the mordenite in a0.2N hydrochloric acid solution at 50° C. for 4 hours with anapproximate H_(s) ⁺ /Al_(z) ratio of 10.

The thus obtained mordenite has a skeleton Si/Al atomic ratio of 7.5.Its sodium weight content is below 300 ppm. Its unit cell volume is 2.76nm³. Its benzene adsorption capacity is 8% by weight, based on the drymordenite weight and its 1,3,5-trimethylbenzene adsorption capacity is1.8% by weight, based on the dry mordenite weight.

The stages of mordenite-alumina mixing, platinum dispersion, shaping,calcination, catalyst reduction and isomerization test conditions arethe same as those described for Example 1. The performancecharacteristics of the catalyst B are given in Table I.

EXAMPLE 3 Catalyst C according to the invention

Catalyst C differs from catalyst A prepared in Example 1 in thatfollowing the third cation exchange (and water washing), the soliddirectly undergoes acid action: It is refluxed in a 0.3N hydrochloricacid solution at 90° C. for 2 hours with an approximate H_(s) ⁺ /Al_(z)ratio of 10.

The thus obtained mordenite has a skeleton Si/Al atomic ratio of 7.6.Its sodium weight content is below 300 ppm. Its unit cell volume is 2.76nm³. Its benzene adsorption capacity is 8.1% by weight, based on the drymordenite weight and its 1,3,5-trimethylbenzene adsorption capacity is1.75% by weight, based on the dry mordenite weight.

The stages of mordenite-alumina mixing, platinum dispersion, shaping,calcination, catalyst reduction and the isomerization test conditionsare the same as those described in Example 1. The performancecharacteristics of the catalyst C are given in Table I.

EXAMPLE 4 Catalyst D, not according to the invention

Catalyst D contains a zeolite of structure MFI, synthesized in afluoride medium. This zeolite has a skeleton Si/Al atomic ratio of 250.Its sodium weight content is 50 ppm. Its unit cell volume is 5.36 nm³.Its benzene adsorption capacity is 9.5% by weight, based on the dryzeolite weight and its 1,3,5-trimethylbenzene adsorption capacity is1.5% by weight, based on the dry zeolite weight.

The stages of zeolite-alumina mixing, platinum dispersion, shaping,calcination, catalyst reduction and the isomerization test conditionsare identical to those described in Example 1, but with a pph of 30(hours)⁻¹. The performance characteristics of catalyst D are given inTable I.

EXAMPLE 5 Catalyst E, not according to the invention

Catalyst E (described in European patent application EP-A-196965)differs from catalyst A prepared in Example 1 in that after the thirdcation exchange (and water washing), the solid is filtered and undergoescalcination in a confined atmosphere (self-steaming) at 600° C. and for2 hours (the calcination atmosphere containing at least 5% steam). Thisis followed by acid action, the solid being refluxed in a 0.6Nhydrochloric acid solution at 90° C. for 2 hours, with a vol/wt ratio of8, in which vol is the volume of the hydrochloric acid solution and wtthe dry mordenite weight. The product is then filtered, washed with 0.1Nhydrochloric acid and then with water.

The thus obtained mordenite has a skeleton Si/Al atomic ratio of 12. Itssodium weight content is approximately 300 ppm. Its unit cell volume is2.75 nm³. Its benzene adsorption capacity is 9.6% by weight, based onthe dry mordenite weight and its 1,3,5-trimethylbenzene adsorptioncapacity is 8% by weight, based on the dry mordenite weight. This meansthat the small pore mordenite is completely unblocked and is equivalentto a large pore mordenite from the adsorption capacity standpoint.

The stages of mordenite-alumina mixing, platinum dispersion, shaping,calcination, catalyst reduction and the isomerization test conditionsare identical to those described in Example 1. The performancecharacteristics of catalyst E appear in Table I.

Catalyst A,B and C according to the invention have better performancecharacteristics than the prior art catalysts D and E. The isomerizationyield of catalysts A, B and C is higher than that of catalysts D and E.Indeed catalyst D is much less active than catalysts A, B and C andcatalyst E has a very limited selectivity.

                  TABLE I                                                         ______________________________________                                                      CATALYST                                                                      A    B       C      D     E                                                   Example                                                                       1    2       3      4     5                                     ______________________________________                                        pph (h.sup.-1)  50     50      50   30    50                                  o-xylene conversion (%)                                                                       58.0   57.5    58.0 50.0  79.5                                isomerization selectivity (%)                                                                 80.0   81.2    79.5 91.5  27.0                                isomerization yield (%)                                                                       46.4   46.7    46.1 45.7  21.5                                dismutation selectivity (%)                                                                    6.5    6.6     6.4  5.5  55.0                                cracking selectivity (%)                                                                       1.5    1.5     1.6  0.8   1.7                                ______________________________________                                    

We claim:
 1. A process for isomerization of a C₈ -aromatic fraction,comprising subjecting said fraction to isomerization conditions in thepresence of a catalyst comprising a mordenite and at least one metalfrom group VIII of the periodic classification of elements, wherein saidmordenite is such that its skeleton Si/Al atomic ratio is between 6 and10.5, its sodium weight content is below 2000 ppm, its unit mesh volumeis between 2.73 and 2.78 nm³, its benzene adsorption capacity is between4 and 10% by weight, based on the dry mordenite weight and its1,3,5-trimethylbenzene adsorption capacity is between 0.5 and 2.5% byweight, based on the dry mordenite weight.
 2. A process according toclaim 1, wherein said mordenite is such that its benzene adsorptioncapacity is between 5 and 9% by weight, based on the dry mordeniteweight and its 1,3,5-trimethylbenzene adsorption capacity is between 0.7and 2% by weight, based on the dry mordenite weight.
 3. A processaccording to claim 1, wherein said mordenite is such that its skeletonSi/Al atomic ratio is between 6 and 9.5 and its sodium weight content isbelow 1000 ppm.
 4. A process according to claim 1 in which the metal isplatinum or palladium.
 5. A process according to claim 1, furthercomprising a matrix.
 6. A process according to claim 1, wherein thecatalyst is prepared from a small pore mordenite having a skeleton Si/Alatomic ratio between 4.5 and 6.5, a sodium weight content between 4 and6.5%, a unit cell volume between 2.77 and 2.80 nm³, said small poremordenite only adsorbing molecules with a kinetic diameter belowapproximately 4.4×10⁻¹⁰ m, the process comprising:(a) at least oneexchange of the sodium cations of the small pore mordenite by ammoniumcations, (b) a solid obtained in stage a) is subjected to a calcinationunder a dry air stream, having a water weight content below 1%, under anair flow rate between 1 and 5 liters/hour/gram of solid, at atemperature between approximately 450° and 650° C., with a temperaturerise rate between 2° and 8° C./minute, the final calcination temperaturebeing maintained for approximately 0.5 to approximately 5 hours.
 7. Aprocess according to claim 6 in which a solid obtained in stage (b) isheated in a mineral or organic acid solution with a normality below0.5N, at a temperature below approximately 60° C., with a H_(s) ⁺/Al_(z) ratio between 8.5 and 11.5, in which H_(s) ⁺ is the number ofproton moles in solution and Al_(z) the number of aluminium cation molesin the mordenite.
 8. A process according to claim 1, wherein thecatalyst is prepared from a small pore mordenite having a skeleton Si/Alatomic ratio is between 4.5 and 6.5, a sodium weight content is between4 and 6.5%, a unit cell volume is between 2.77 and 2.80 nm³, said smallpore mordenite only adsorbing molecules with a kinetic diameter belowapproximately 4.4×10⁻¹⁰ m, the process comprising:(a) at least oneexchange of the sodium cations of the small pore mordenite by ammoniumcations, (b) a solid obtained in stage (a) is heated to a temperatureabove approximately 85° C. in a solution of a mineral or organic acidwith a normality between 0.2 and 3N, with a H_(s) ⁺ /Al_(z) ratiobetween 8 and 15, in which H_(s) ⁺ is the number of proton moles in thesolution and Al_(z) the number of aluminium cation moles in themordenite.
 9. A process according to claim 5, wherein the matrix isalumina.